CN103314018A - Polyvinyl alcohol resin and method for producing same - Google Patents
Polyvinyl alcohol resin and method for producing same Download PDFInfo
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- CN103314018A CN103314018A CN201180065169XA CN201180065169A CN103314018A CN 103314018 A CN103314018 A CN 103314018A CN 201180065169X A CN201180065169X A CN 201180065169XA CN 201180065169 A CN201180065169 A CN 201180065169A CN 103314018 A CN103314018 A CN 103314018A
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- polyvinyl alcohol
- pva resin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F16/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F16/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F16/04—Acyclic compounds
- C08F16/06—Polyvinyl alcohol ; Vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/008—Treatment of solid polymer wetted by water or organic solvents, e.g. coagulum, filter cakes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/002—Methods
- B29B7/007—Methods for continuous mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/82—Heating or cooling
- B29B7/826—Apparatus therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F18/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F18/02—Esters of monocarboxylic acids
- C08F18/04—Vinyl esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
- C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
- C08F216/04—Acyclic compounds
- C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F6/00—Post-polymerisation treatments
- C08F6/06—Treatment of polymer solutions
- C08F6/10—Removal of volatile materials, e.g. solvents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2329/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
- C08J2329/02—Homopolymers or copolymers of unsaturated alcohols
- C08J2329/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
Abstract
Provided are a polyvinyl alcohol resin superior in handling and less prone to generate dissolution residue when dissolved in water, and a method for producing the same. A polyvinyl alcohol resin slurry obtained through a polymerization step (step S1) and a saponification step (step S2) is heated to 100 DEG C to 170 DEG C and volatile components contained therein are brought to 1 mass% or lower (step S3). Thereafter, the resin from which the volatile components have been removed is extrusion-molded into a strand shape using a die provided with a hole having a diameter of 3 to 8 mm[mu]m, and the extrusion-molded resin is air-cooled or wind-cooled until the temperature reaches 45 DEG C or lower (step S4). Then, the cooled resin is pulverized into rod-shaped particles having a length of 1 to 10 mm and maximum diameter of 0.5 to 3.0 mm (step S5).
Description
Technical field
The present invention relates to polyvinyl alcohol resin and preparation method thereof.More refer in detail to and when the preparation vinyl chloride resin, be used as polyvinyl alcohol resin of dispersion agent and preparation method thereof.
Background technology
Polyvinyl alcohol (PVA) is water miscible synthetic resins, utilizes its feature and makes it be used for various fields such as thin-film material, emulsifying dispersant, tackiness agent and adhesive resin.This PVA resin is by the polymerization vinyl acetate monomer, resulting polyvinyl acetate is carried out saponification prepare, and generally can use Powdered or granular resin (with reference to patent documentation 1～4).For example, in patent documentation 1,2, disclose a kind of in order to improve the dispersiveness of water and the particle diameter of PVA is made PVA particulate below several μ m.
On the other hand, in patent documentation 3,4, disclose and a kind ofly made particle diameter more than hundreds of μ m and then make sheet more than several mm or the PVA resin of pill shape.In the preparation method of the PVA resin pellet that this patent documentation 4 is put down in writing; it is in 9.3～14.4 the solidification liquid that the water/alcohol mixed solution that will comprise the PVA resin behind the saponifying process is expressed into solubility parameter δ, and with tablets press etc. resulting line is cut off and make pill.
[prior art document]
[patent documentation]
Patent documentation 1: Japanese kokai publication hei 11-236417 communique
Patent documentation 2: TOHKEMY 2006-89536 communique
Patent documentation 3: the flat 11-504374 communique of Japanese Unexamined Patent Application Publication
Patent documentation 4: TOHKEMY 2002-301715 communique
Summary of the invention
Invent problem to be solved
Yet the PVA resin micropowder as patent documentation 1,2 is put down in writing because its surface-area is big, and condenses easily when being dissolved in water, and because it disperses easily the problem of operability difference is arranged.On the other hand, the technology that patent documentation 3 is put down in writing, because being purpose to obtain sheet PVA resin, thereby the pulverizing part of resulting PVA resin contacts each other and produces the problem of caking when having.
In addition, the preparation method of the PVA resin pellet that patent documentation 4 is put down in writing is that water/ethanolic soln with the PVA resin is expressed in the solidification liquid of acetone or methyl ethyl ketone etc. and after it is solidified, resulting pill is cleaned, and made its drying.Therefore, the preparation method that puts down in writing of this patent documentation 4 residue that can produce solidification liquid be attached to resulting pill surface problem, need the problem of equipment such as precipitation bath or drying machine.
Therefore, main purpose of the present invention is, a kind of operability polyvinyl alcohol resin good and difficult generation dissolution residual substance when being dissolved in water and preparation method thereof is provided.Be used for solving the means of problem
Polyvinyl alcohol resin of the present invention is that length is that 1～10mm, maximum diameter are the rod-shaped particle of 0.5～3.0mm.
In the present invention, because polyvinyl alcohol resin being made the rod-shaped particle of specific dimensions, and can not produce dust, improve resistance to blocking yet.And, also accelerated the dissolution rate to water.
The preparation method of polyvinyl alcohol resin of the present invention has following operation: polyvinyl ester is carried out saponification and the polyvinyl alcohol resin slurries that obtain are heated to 100～170 ℃, and to make the volatile component that contains be the following desolventizing operation of 1 quality %; Use possesses the mould that diameter is the hole of 1～15mm, the resin extruded behind the removal volatile component is shaped to the operation of wire; Resin after the extrusion molding is carried out air cooling or air-cooled until the operation that reaches 45 ℃ of following temperature; And cooled resin is pulverized and obtained length is that 1～10mm, maximum diameter are the operation of the rod-shaped particle of 0.5～3.0mm.
In the present invention, because not using solidification liquid, prepare the polyvinyl alcohol resin of specified particle shape by melted extrusion modeling, so can obtain not having the residue of solidification liquid to adhere to, to the solvability of water and operability good polyvinyl alcohol resin all.
This preparation method also can stir while reducing pressure when removing volatile component.
The effect of invention
According to the present invention, because polyvinyl alcohol resin being made the rod-shaped particle of specific dimensions, so except improving the solvability that can also improve the operability water.
Description of drawings
Fig. 1 is preparation method's the schema of the PVA resin of expression embodiment of the present invention.
Embodiment
Below, with reference to accompanying drawing, describe the enforcement mode of the present invention that is used in detail.In addition, the present invention is not limited to following illustrated embodiment.The polyvinyl alcohol of embodiment of the present invention (PVA) resin is rod-shaped particle, and its length is that 1～10mm, maximum diameter are 0.5～3.0mm.
［ shape ］
Existing powdery PVA resin is big because of surface-area, is condensed into piece easily when being dissolved in water, and the problem that is difficult for being dissolved in water is arranged, or because light specific gravity disperses easily, and the problem of operability difference is arranged.On the other hand, to the big PVA resin of particle diameter carry out pulverization process and the pill of the indefinite shape that obtains because having size-grade distribution, also comprise the big pill of granularity, so according to dissolution conditions the incomplete situation of PVA resin dissolves is arranged.In addition, the pill of this indefinite shape can produce the situation that resin stops up or lumps, so operability is also poor because pulverizing partly contact each other in pipe arrangement.
With respect to this, because the PVA resin of present embodiment is rod-shaped particle, surface-area is also little, and particle contact area each other is also few, thus dissolve easily in water, and be difficult for producing caking.Therefore, compare with the crushed material of above-mentioned powdery or indefinite shape, can improve solvability and operability to water.
［ length ］
The length of the PVA resin of present embodiment is 1～10mm.Thus, be difficult for producing caking, and when being dissolved in water, be difficult for producing dissolution residual substance.In addition, under the situation of particle length less than 1mm of PVA resin, with respect to the ratio step-down of the particle side in cross section, thereby be easy to generate caking.On the other hand, if the particle length of PVA resin surpasses 10mm, then when being dissolved in water, produce dissolution residual substance sometimes.
［ maximum diameter ］
The maximum diameter of the PVA resin of present embodiment is 0.5～3.0mm.Thus, be difficult for producing caking, when being dissolved in water, can suppress dissolution residual substance simultaneously.In addition, under the situation of maximum diameter less than 0.5mm of PVA resin, the PVA resin becomes and lumps easily, in addition, if surpass 3.0mm, then produces the residual particle of dissolving sometimes in water.
The preparation method of the PVA resin of present embodiment is described then.Fig. 1 is preparation method's the schema of the PVA resin of expression present embodiment.As shown in Figure 1, the preparation method of the PVA resin of present embodiment is to implement each operation with the order of polymerization process (step S1), saponifying process (step S2), desolventizing operation (step S3), refrigerating work procedure (step S4) and pulverizing process (step S5).
［ polymerization process ］
The polymerization process of step S1 is to make one or more vinyl acetate carry out polymerization or make vinyl acetate and can carry out copolymerization with other monomer of its copolymerization and obtain polyvinyl ester.Vinyl acetate as used herein for example comprises vinyl formate, vinyl-acetic ester, propionate, valeric acid vinyl acetate, capric acid vinyl acetate, vinyl laurate, stearic acid vinyl ester, vinyl benzoate, trimethylacetic acid vinyl acetate and tertiary ethylene carbonate (vinyl versatate) etc., from the viewpoint of polymerization stability, special preferred vinyl-acetic ester.
In addition, for being not particularly limited with other monomer that these vinyl acetate are carried out copolymerization, for example comprise: alpha-olefines such as ethene and propylene; (methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) butyl acrylate and (methyl) ethyl acrylate; Unsaturated acyl amines such as (methyl) acrylamide and N hydroxymethyl acrylamide; Unsaturated acids such as (methyl) vinylformic acid, Ba Dousuan, toxilic acid, methylene-succinic acid and fumaric acid; The salt (sodium salt, sylvite, ammonium salt etc.) of unsaturated acid anhydrides such as the alkyl of unsaturated acid (methyl, ethyl, propyl group etc.) ester, maleic anhydride, unsaturated acid; Glycidyl allyl ether, (methyl) glycidyl acrylate etc. contain the monomer of glycidyl; 2-acrylamide-2-methyl propane sulfonic acid and its esters etc. contain sulfonic monomer; Methacrylic acid acid phosphorus oxygen base ethyl ester (acid phosphoxyethyl methacrylate) and methacrylic acid acid phosphorus oxygen base propyl ester (acid phosphoxypropyl methacrylate) etc. contain the monomer of phosphate; Alkyl vinyl ethers etc.
［ saponifying process ］
The saponifying process of step S2 is in organic solvent and in the presence of catalyzer, and the resulting polyvinyl ester of step S1 is carried out saponification.At this moment, organic solvent can use alcohols such as methyl alcohol, ethanol, propyl alcohol, ethylene glycol, propylene glycol, glycerol and Diethylene Glycol, special particular methanol.
In addition, as the saponification catalyzer, for example comprise alkaline catalystss such as sodium hydroxide, potassium hydroxide, sodium alkoxide and yellow soda ash; Acid catalysts such as sulfuric acid, phosphoric acid and hydrochloric acid.In these saponification catalyzer, preferably use alkaline catalysts, more preferably use sodium hydroxide.Thus, can accelerate saponification speed and productivity is improved.
By this saponifying process, part or all that makes vinyl acetate unit in the polyvinyl ester carried out saponification, becomes vinyl alcohol units.In addition, the saponification deg by the resulting PVA resin of above-mentioned saponifying process is not particularly limited, can suitably sets according to purposes etc.
［ desolventizing operation ］
Then, remove the saponification solvent the PVA resin slurries under comprising the resulting saponification solvent of step S2 state, and to make the amount of volatile component contained in the PVA resin (saponification solvent) be 1 quality % following (step S3).Its concrete method is not particularly limited, and suitably application examples is as using the method that slurries are stirred on decompression type kneading machine etc., limit, heat on the limit and reduce pressure.
In addition, if the residual volatile component that has above 1 quality % in the PVA resin behind desolventizing, then in pulverizing process described later, line becomes and is difficult for pulverizing, position beyond perhaps at desired position cuts off line, thereby makes the shape of resulting PVA resin produce deviation etc.
In addition, though the Heating temperature of this moment can suitably be set according to the saponification solvent types, be preferably 100～170 ℃.Thus, the amount of volatile component can be fully removed, and the flavescence of resulting PVA resin can be prevented.In addition, Heating temperature less than 100 ℃ situation under, the content of volatile component does not fully reduce, if surpass 170 ℃, then the resulting PVA resin of slurries thermal degradation can flavescence.
［ moulding/refrigerating work procedure ］
Moulding/refrigerating work procedure of step S4 is to use for example possesses the mould that a plurality of diameters are the hole of 3～8mm, with the PVA resin that carries out among the step S3 behind the desolventizing, extrusion molding is after the wire on endless belt conveyor, in mounting under the state on the endless belt conveyor, in atmosphere, carry out air cooling or air-cooled be (step S4) below 45 ℃ until resin temperature.Thus, having obtained maximum diameter is the microscler bar-shaped resin (line) of 0.5～3.0mm.
In addition, the cooling of line can slowly be cooled off at endless belt conveyor, and also the cooling air that oppositely blows of travel direction that can be along the line carries out air cooling.In addition, the line of extruding by mould is stretched by endless belt conveyor or pulverizer sometimes, thereby becomes also thinner than the aperture of mould.
［ pulverizing process ］
Then, use pulverizers such as tablets press, with the microscler bar-shaped resin (line) that carries out among the step S4 after the moulding, being ground into length is 1～10mm(step S5).Pulverization conditions to this moment is not particularly limited, and can use the rotating knife that for example has eight blades, and the pulling speed of the line that divides with 1～25m/ is pulverized.At this moment, if pulling speed is too fast, then because of the impact of the rotating knife that is delivered to line, can make the cut surface roughen of resulting rod-shaped particle, produce the reason of luming and become.
Like this, in the PVA of present embodiment resin, be that 1～10mm, maximum diameter are the bar-shaped of 0.5～3.0mm because particle shape being made length, so enhanced dissolution rate to water, in addition, compare with the powdery product in past, (blocking resistance) is good for the resistance to blocking of the PVA resin of present embodiment, also can not produce dust.In addition, the size-grade distribution of the PVA resin of present embodiment is narrow, size is consistent.Consequently, obtain also good PVA resin of the good and operability of solvability to water.Because this characteristic, the PVA resin of present embodiment is particularly suitable as the dispersion agent when the suspension polymerized vinyl chloride resin.
[embodiment]
Below enumerate embodiments of the invention and comparative example, specifically describe effect of the present invention.In the present embodiment, a plurality of PVA resin particles that made shape, vary in size have been estimated its solvability and operability.Each PVA resin particle of embodiment and comparative example all uses identical PVA resin slurries, and makes by following method.
＜PVA slurries＞
With 10 mass parts vinyl-acetic esters, 17 mass parts methyl alcohol, be injected in the polymerization tank with respect to the Diisopropyl azodicarboxylate of 0.10 quality % of vinyl-acetic ester.Then, after in the nitrogen replacement jar, carry out heat temperature raising to boiling point, and then, on one side add 3.5 mass parts vinyl-acetic esters and 7.5 mass parts methyl alcohol continuously mixed solution carry out polymerization on one side and reach 75% until percent polymerization, reach at 90% o'clock at percent polymerization and stop polymerization.
, with common method remove unpolymerized vinyl-acetic ester, obtained the methanol solution of polyvinyl acetate (hereinafter referred to as PVAc) base polymer thereafter.Then, get this solution of a part, carry out saponification with common method, obtained viscosity average polymerization degree and be 400, saponification deg is that 50mol%, solids concn are 45% PVA resin slurries.
＜PVA resin particle＞
(embodiment 1)
130 ℃ ,-under the condition of 0.06MPa, after above-mentioned PVA resin slurries are carried out drying under reduced pressure, passed through to possess diameter and be 3mm the hole mould and extrude, pulling speed with the 20m/ branch, resulting line is pulverized, and having obtained length is that 5mm, diameter are the bar-shaped PVA resin particle of 0.5mm.In addition, KRC kneading machine (tremble this ironworker society make) has all been used in drying under reduced pressure and extrusion molding.All identical in following embodiment and comparative example.
(embodiment 2)
130 ℃ ,-under the condition of 0.06MPa, after above-mentioned PVA resin slurries are carried out drying under reduced pressure, passed through to possess diameter and be 5mm the hole mould and extrude, pulling speed with the 20m/ branch, resulting line is pulverized, and having obtained length is that 5mm, diameter are the bar-shaped PVA resin particle of 1.0mm.
(embodiment 3)
130 ℃ ,-under the condition of 0.06MPa, after above-mentioned PVA resin slurries are carried out drying under reduced pressure, passed through to possess diameter and be 8mm the hole mould and extrude, pulling speed with the 20m/ branch, resulting line is pulverized, and having obtained length is that 5mm, diameter are the bar-shaped PVA resin particle of 3.0mm.
(embodiment 4)
130 ℃ ,-under the condition of 0.06MPa, after above-mentioned PVA resin slurries are carried out drying under reduced pressure, passed through to possess diameter and be 4mm the hole mould and extrude, pulling speed with the 5m/ branch, resulting line is pulverized, and having obtained length is that 10mm, diameter are the bar-shaped PVA resin particle of 1.0mm.
(embodiment 5)
130 ℃ ,-under the condition of 0.06MPa, after above-mentioned PVA resin slurries are carried out drying under reduced pressure, passed through to possess diameter and be 6mm the hole mould and extrude, pulling speed with the 24m/ branch, resulting line is pulverized, and having obtained length is that 1mm, diameter are the bar-shaped PVA resin particle of 1.0mm.
(comparative example 1)
130 ℃ ,-under the condition of 0.06MPa, after above-mentioned PVA resin slurries are carried out drying under reduced pressure, passed through to possess diameter and be 7mm the hole mould and extrude, pulling speed with the 30m/ branch, resulting line is pulverized, and having obtained length is that 0.5mm, diameter are the bar-shaped PVA resin particle of 1.0mm.
(comparative example 2)
130 ℃ ,-under the condition of 0.06MPa, after above-mentioned PVA resin slurries are carried out drying under reduced pressure, passed through to possess diameter and be 3mm the hole mould and extrude, pulling speed with the 0.9m/ branch, resulting line is pulverized, and having obtained length is that 15mm, diameter are the bar-shaped PVA resin particle of 1.0mm.
(comparative example 3)
130 ℃ ,-under the condition of 0.06MPa, after above-mentioned PVA resin slurries are carried out drying under reduced pressure, passed through to possess diameter and be 1mm the hole mould and extrude, pulling speed with the 20m/ branch, resulting line is pulverized, and having obtained length is that 5mm, diameter are the bar-shaped PVA resin particle of 0.3mm.
(comparative example 4)
130 ℃ ,-under the condition of 0.06MPa, after above-mentioned PVA resin slurries are carried out drying under reduced pressure, passed through to possess diameter and be 9mm the hole mould and extrude, pulling speed with the 20m/ branch, resulting line is pulverized, and having obtained length is that 5mm, diameter are the bar-shaped PVA resin particle of 3.5mm.
＜solvability＞
The pure water of 23 ℃ of the PVA resin particle of 5 mass parts embodiment or comparative example and 95 mass parts is put in the separating flask of 1L, is 200rpm with the stirring velocity, utilizes anchor stirrer to stir, and has measured the time till the PVA resin dissolves fully.In addition, the maximum duration of instrumentation time is 60 minutes.
＜operability＞
The pure water of 23 ℃ of the PVA resin particle of 5 mass parts embodiment or comparative example and 95 mass parts is put in the separating flask of 1L, be 200rpm with the stirring velocity, utilize anchor stirrer to stir 50 minutes and regulated to obtain solution, and this solution is circulated, thereby confirmed that in pipe inside whether resin taking place stops up (caking) in the pipe of the stainless steel of internal diameter 5mm.
In following table 1, gather and represented above result.
[table 1]
Shown in above-mentioned table 1, length less than the PVA resin of the comparative example 1 of 1mm and maximum diameter less than the PVA resin of the comparative example 3 of 0.5mm when being dissolved in water, particle can condense, and then has also produced caking.In addition, though length is good greater than the PVA resin operability of the comparative example 4 of 3.0mm greater than PVA resin, the maximum diameter of the comparative example 2 of 10mm, when being dissolved in water, produced dissolution residual substance.
With respect to this, PVA dissolving resin and the operability of the whole embodiment 1～5 within the scope of the present invention of the length of rod-shaped particle, maximum diameter and granularity are all good.
Claims (4)
1. polyvinyl alcohol resin, it is that length is that 1～10mm, maximum diameter are the rod-shaped particle of 0.5～3.0mm.
2. the preparation method of a polyvinyl alcohol resin has following operation:
The polyvinyl alcohol resin slurries that polyvinyl ester carried out saponification and obtain are heated to 100～170 ℃, and to make the volatile component that contains be the following operation of 1 quality %;
Use possesses the mould that diameter is the hole of 3～8mm, the resin extruded behind the removal volatile component is shaped to the operation of wire;
Resin after the extrusion molding is carried out air cooling or air-cooled until the operation that reaches 45 ℃ of following temperature;
And cooled resin is pulverized and obtained length is that 1～10mm, maximum diameter are the operation of the rod-shaped particle of 0.5～3.0mm.
3. the preparation method of polyvinyl alcohol resin as claimed in claim 2 is characterized in that, when removing volatile component, stirs while reduce pressure.
4. as the preparation method of claim 2 or 3 described polyvinyl alcohol resins, it is characterized in that, the resin of removing behind the volatile component carried out extrusion molding on tape, described with on the resin after the moulding is carried out air cooling or air-cooled.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-007674 | 2011-01-18 | ||
| JP2011007674A JP5498402B2 (en) | 2011-01-18 | 2011-01-18 | Method for producing polyvinyl alcohol resin |
| PCT/JP2011/075169 WO2012098748A1 (en) | 2011-01-18 | 2011-11-01 | Polyvinyl alcohol resin and method for producing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103314018A true CN103314018A (en) | 2013-09-18 |
| CN103314018B CN103314018B (en) | 2015-11-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180065169.XA Active CN103314018B (en) | 2011-01-18 | 2011-11-01 | Polyvinyl alcohol resin and preparation method thereof |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5498402B2 (en) |
| KR (1) | KR101813855B1 (en) |
| CN (1) | CN103314018B (en) |
| TW (1) | TWI513711B (en) |
| WO (1) | WO2012098748A1 (en) |
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| JP6381964B2 (en) * | 2014-05-12 | 2018-08-29 | 日本合成化学工業株式会社 | Polyvinyl alcohol resin pellet manufacturing method |
| TWI522373B (en) * | 2015-01-27 | 2016-02-21 | 長春石油化學股份有限公司 | Polyvinyl alcohol and purification method thereof |
| US11718010B2 (en) | 2020-05-26 | 2023-08-08 | Peter Morris Research And Development Limited | Method of making a water-soluble polymer composition |
| CA3184903A1 (en) * | 2020-05-26 | 2021-12-02 | Peter Morris Research And Development Limited | Method of making a water-soluble polymer, water-soluble polymer so produced, and melt-processable water-soluble polymer composition |
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| EP1120436A1 (en) * | 1999-05-24 | 2001-08-01 | Hosokawa Micron Corporation | Method for forming granule of thermoplastic resin |
| JP2002301715A (en) * | 2001-04-06 | 2002-10-15 | Nippon Synthetic Chem Ind Co Ltd:The | Method for manufacturing polyvinyl alcohol based resin pellet |
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| DE19835744A1 (en) * | 1998-08-07 | 2000-02-17 | Bayer Ag | Process for evaporating polymer solutions of thermoplastic polymers |
| JP2000169592A (en) * | 1998-12-10 | 2000-06-20 | Teijin Chem Ltd | Production of polycarbonate resin granule |
| JP4527818B2 (en) * | 1999-03-16 | 2010-08-18 | 日本合成化学工業株式会社 | Saponified pellet of ethylene-vinyl acetate copolymer |
| JP4081530B2 (en) * | 2001-10-31 | 2008-04-30 | 日本合成化学工業株式会社 | Saponified pellet of ethylene-vinyl acetate copolymer |
| TWI256954B (en) * | 2003-01-30 | 2006-06-21 | Nippon Synthetic Chem Ind | Dispersing agent comprising vinyl alcohol polymer having conjugated double bonds in its molecule |
| JP4087321B2 (en) * | 2003-09-17 | 2008-05-21 | 株式会社クラレ | POLYVINYL ALCOHOL POLYMER AND PROCESS FOR PRODUCING THE SAME |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1120436A1 (en) * | 1999-05-24 | 2001-08-01 | Hosokawa Micron Corporation | Method for forming granule of thermoplastic resin |
| JP2002301715A (en) * | 2001-04-06 | 2002-10-15 | Nippon Synthetic Chem Ind Co Ltd:The | Method for manufacturing polyvinyl alcohol based resin pellet |
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| KR101813855B1 (en) | 2017-12-29 |
| KR20140012050A (en) | 2014-01-29 |
| TW201231477A (en) | 2012-08-01 |
| JP2012149144A (en) | 2012-08-09 |
| JP5498402B2 (en) | 2014-05-21 |
| WO2012098748A1 (en) | 2012-07-26 |
| CN103314018B (en) | 2015-11-25 |
| TWI513711B (en) | 2015-12-21 |
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